Process of producing tannin and the product.



'- srATEs PATENT OFICE.

crnm'rns runners ALLEN; or NEW nmanroufunw YORK.

. mousse-or rnonuomerau-nm AND run rnonucr.

No Drawings specification of Letters Patent. Patented N av, 18, 19 13..

product, that is tannin substantially free from acid, and a process by which that product may be secured. 1

Tannm is a substance which has, long been known and widely used, but so far as I am conversant with the varieties 'earlier'pro,

duced, they invariably contained an acid, usually gallotannic acid.

By producing tannin. from. the. envelops,

hulls or shells of pecanrlj uta also' known as Gar ya OZZ'YUW form's, using a process, devised by me,:I have produceda tannin which I be lieve. has new and valuable properties, or more strictl speaking is without those objec' tionab e characteristics which the ordinary tannins of commerce possess, the most important of which is that already'noted.

The new product which I have discovered may be recognized by its reactions shown by testing with various substances. For instance this tannin when tested with bromin watenproducesa precipitate, though it is not peculiar-in that, but other tests show difierencesover other tannins. Iron alum gives a. greenprecipitate, sodiumnitrate and N-10HC1 gives pink precipitate; cupric sulfate, gives. no change in color; cupric sulfate followed by ammonia gives a decidcd blue precipitate; ferrous sulfate gives a black precipitate; fcrric sulfate gives a greenish black precipitate; stannous chlorid and concentrated hydrochloric acid gives a yellowish color; sodium sulfite gives no change; concentrated sulfuric acid gives, on standing, a precipitate though at first it is only cloudy; lime water gives a' dark gray precipitate; ammonium vanadate gives a light blue color; ferric acetate gives a. dark black precipitate; cupric acetate gives a brown precipitate; cupric acetate with the subsequent addition of ammonium carbonategives a blue precipitate.

It \will be noted that the test with lime water gives a dark gray precipitate and not the dark brown precipitate which would in dicate the presence of elagic acid, that the test with iron alum produces a green pre- I Application filed January 5, 1912.: Serial mi. 669 559.

c'ipitate and not the blue black precipitate which occurs when gallic acid is present; also that the test, with, sodium .sulfi-te produces no change'and not the gradual change which the presence of galli'c acid would.

cause. I am confident therefore in my belief that my product is, as stated,"sub stantially free from acidand that isanew product.

This, product I I have lining. of the shells), I grind such material 1 to fine. powder; preferably such as will pass through a 30 mesh sieve, then I make an infusion of this powderwith boiling water,

using one gallon of water to two pounds of the powdered shells and preferably pouring the boiling water over the powderedshells, as this is easier than to put the powder into the water and mix them together. The infusion is permitted to stand until cool, when some of the" still solid particles will'have settled to thebottom of the containing vessel. I then decant the clear liquor, place the residuum in a percolator, packing it tightly therein, and pour over it a quantlty of alco hoLusing about 4 ounces of alcohol to each two poundsof the original quantity of the powder. After pouring in the alcohol, I pour in the clear liquid, which was decanted as aforesaid, and let the mixture percolate. If the resultant liquor is less than a gallon per two pounds of original powder, I usually pour more'water into the percolator, until the quantity of percolated liquor is equal to one gallon per two pounds of original powder. When the percolation has terminated, the percolated liquor is ready for use in tanning very fine qualities of leather and will be found to consist of a varietv or quality of tannin not heretofore obtained and to be free from many ingredients which are deleteriousin tanning fine leathers, but which are ordinarily associated with other tanning substances.

The percentages named are, asstated, preferential, but I may vary them consider-- ably since a greater quantity of'water will produce a tannin solutibn, but it will be weaker than usually desired, but nevertheless a good tannin for some uses. -So too a smaller quantity of water Will produce a tannin, but not as much as may be. produced produced as 01 lows :Havingselected a. quantity of the shells or coverings enveloping and protecting the meatof the pecan nut, (takingcare to include as much as possible of the interior from the basic material when the preferred proportions are employed, nevertheless I may use more or less water and more or, less alcohol, one particular advantage of the latter being that it will prevent the solution from spoiling.

I find that I get my best results when I use the water at the boiling point.

Some success may. be attained by using benzin, chloroform, ether, alcohol, gasolene, naphtha or glycerin for the firstdilunt, in place of' water, the quantity being preferably about the same, in proportion, as the water, but the water is important at some step of my process and if I did not use it in the so- 7 lution, then I would use it in the 'drench whichv I use afterpa'cking the first residuum in the percolator.

There have been tannins produced heretofore, which were called pure tannins, but I know of no one of, them which does not show, on test, that gallic or gallotannic acid is present. short, tannin without such acid or other elements equally objectionable does not seem to exist as an independent natural substance. I have succeeded in-so dividing and combining the composition of matter grown as a pecan nut shell, that I have produced what I-te'rm a pure tannin,

but which. differs, as noted from earlier products.

v f What I claim and desire to secure by Letters Patent is '1.' As anew composition of matter, pecan nutshell tannin possessing the herein described characteristics, practically free from acids and free from the woody constituents of the shells and giving reactions under various tests jsuch as'follows; with iron alum,a greenprecipitate; sodium nitrate, a ,pinkl precipitate; cupric sulfate, no change in color; cupric sulfate followed by ammonia,', a decided blue; ferrous sulfate, a black p cipitate; ferricsulfate, a greenish blac preeioitate; stannous chlorid and concentrat'ed hydrochloric acid, a yellowish color ,sodium sulfite, no change in color; conc'e fated sulfuricacid, a precipitate, on standing? ferric acetate, a dark black precipitate; cupric acetate, a brown precipitate;

- cupric a'cetate,"addition of ammonium car bonate, a blue precipitate; all substantially as set forth. v

2. As a new composition of matter, a liquid manufactured from pecan nut shells, water and alcohol, possessing-the herein described characteristics, practically free from acids and free from the woody constituents of the shells and giving reactions under vari- 'oustests,such as'follows; with iron alum, a green precipitate; sodium nitrate, a pink precipitate; cupric sulfate, no change in color; cupric sulfate followed by ammonia, a decided blue; ferrous sulfate, a black precipitate; ferrio'sulfate, a greenish black precipita-te; stannouschlorid and concentrated hydrochloric'acid, a' yellowish color sodium ,sulfite, no change in color; concentrated sulfuric acid, a precipitate, on standing; ferric acetate, a dark blackprecipitate; cupric acetate, a brown precipitate; cupric acetate, addition of ammonium carbonate, a blue precipitate; all substantially as set forth.

3. As a newcomposition of matter, a tannin manufactured from pecan nut shells,

water and alcohol, possessing the herein described characteristics, practically free from acids and free from the woody constituents of the shells and giving reactions under vari ous tests, such as follows; with iron alum, a green precipitate; sodium nitrate, a pink precipitate; cupric sulfate, no change in color; cupric sulfate followed by ammonia,

.a decided blue; ferrous sulfate, a black precipitate; ferric sulfate, a greenish black precipitate; stannous chlorid and concentrated hydrochloric acid, a yellowish color; sodium sulfite, no change in color; concentrated sulfuric acid, a precipitate, on standing; ferrlc ,acetate, a dark black precipitate; cupric acetate, a brown precipitate; cupric acetate, addition of ammonium carbonate, a blue precipitate; all substantially as set forth.

4. As a new composition of inatter, a tannin manufactured from pecan nut shells and possessing the following characteristics in its liquid form, as a solid extract and as a powdered extract, practically free from acids and free from the woody constituents of the shells ahd giving reactions under Various tests, such as follows; with iron alum, a green precipitate, sodium nitrate, a pink precipitate; cupric sulfate: no change in color; cupric sulfate followed by ammonia, a decided blue; ferrous sulfate, a black precipitate; ferric sulfate, a greenish precipitate;

stannous chlorid and concentrated hydrochloric acid, a yellowish color; sodium sulfite, no change in color; concentrated sulfuric acid, a precipitate, on standing; ferric acetate, a dark black precipitate; cupric acetate, a brown precipitate; cupric acetate, addition of'ammonium carbonate, a blue precipitate; all substantially as set forth. 1

5. The process ofproducing a tannin solution possessing the herein described characteristics, which consists in comminuting pecan nut shells, mixing them with water at about the boiling point, allowing the mixture to stand, separating the liquid part, placing the other part in a percolator, adding alcohol and the previously separated liquid and drawing off the percolations, all substantially as set forth.

6. The process of producing a tannin solution, which consists in comminuting pecan nut shellsfmixing them with a liquid tannin solvent, allowing the mixture to stand, separating the liquid part, placing the other part in a percolator, adding alcohol and the previously separated liquid and drawing off the peroola-tions, all substantially as set-forth.

' 7 The process of producing atannin solution, which consists in comminuting'pecan nut shells, mixing them with hot water, 111-- lowingthe mixture to stand and cool,sepa= ratingthe liquid part, plaoing the other part in a percola-tor, adding alcohol and the revirating the liquid part, placing the other pal t' in a'percolator, adding alcohol and the-previously separated liquid and drawing oil the percolations, using substantially the proportions specified to Wit, about two pounds of powdered shells to one gallon of water and 4 ounces ofvalcohol, all substantially asset forth.

In testimony whereof,- I have signed my name to this specification in the presence of two subscribing witnesses, this 2d day of January, 1912. CHARLES FRANCIS ALLEN.

Witnesses:

ALICE M. KEALY, LILA B. \VARREN. 

